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- W2023556181 abstract "Synthesis of stable hydride isocyanide derivatives Nb(η5-C5H4SiMe3)2(H)(CNR) has been achieved through the formation of coordinatively unsaturated 16-electron species Nb(η5-C5H4SiMe3)2H by thermolytic loss of H2 followed by the coordination of an isocyanide ligand. Low-temperature protonation with a slight excess of CF3COOH leads to the η2-dihydrogen complexes [Nb(η5-C5H4SiMe3)2(η2-H2)(CNR)]+. NMR spectra of these H−H complexes and their monodeuterated H−D isotopomers present a single high-field resonance at room temperature. By lowering the temperature to 178 K, decoalescence of the signal was observed for the H−D complexes but not for the H−H ones. By combining DFT electronic structure calculations with a monodimensional rotational tunneling model, it has been shown that the absence of decoalescence of the H−H signal is due to the existence of a very large exchange coupling. Conversely, for the H−D isotopomer, the difference in zero point energy corresponding to two nonequivalent (H−D and D-H) positions leads to a slight asymmetry which dramatically reduces the exchange coupling, allowing decoalescence to be observed. Therefore, the H−D classical rotation and the quantum exchange processes will not be practically observed for this complex, whereas only the classical process for the H−H species is quenched out on the NMR time scale." @default.
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- W2023556181 date "1997-07-01" @default.
- W2023556181 modified "2023-10-17" @default.
- W2023556181 title "Synthesis and Spectroscopic Properties of Dihydrogen Isocyanide Niobocene [Nb(η<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>SiMe<sub>3</sub>)<sub>2</sub>(η<sup>2</sup>-H<sub>2</sub>)(CNR)]<sup>+</sup> Complexes. Experimental and Theoretical Study of the Blocked Rotation of a Coordinated Dihydrogen" @default.
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- W2023556181 doi "https://doi.org/10.1021/ja9640354" @default.
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